JP5948660B2 - Non-aqueous electrolyte and lithium secondary battery including the same - Google Patents

Description

  The present invention relates to a non-aqueous electrolyte containing propylene carbonate (PC) and lithium bis (fluorosulfonyl) imide (LiFSI), and a lithium secondary battery including the same.

  As technology development and demand for mobile devices increase, the demand for secondary batteries as energy sources has increased rapidly, and lithium secondary batteries having the higher energy density and voltage of such secondary batteries. Has been put into practical use and widely used.

  As the positive electrode active material of the lithium secondary battery, lithium metal oxide is used, and as the negative electrode active material, lithium metal, lithium alloy, crystalline or amorphous carbon, or carbon composite is used. The active material is applied to the current collector with an appropriate thickness and length, or the active material itself is applied in the form of a film and wound or laminated together with a separator as an insulator to form an electrode group. After putting it in a similar container, an electrolytic solution is injected to manufacture a secondary battery.

Such a lithium secondary battery is charged and discharged while repeating a process in which lithium ions are intercalated and deintercalated from the lithium metal oxide of the positive electrode into the graphite electrode of the negative electrode. At this time, since lithium is highly reactive, it reacts with the carbon electrode to generate Li ₂ CO ₃ , LiO, LiOH, or the like, and a film can be formed on the surface of the negative electrode. Such a coating is referred to as a solid electrolyte interface (SEI) coating, but the SEI coating formed at the initial stage of charging can prevent the reaction between lithium ions and the carbon negative electrode or other substances during charging and discharging. Also, it can function as an ion tunnel and allow only lithium ions to pass therethrough. This ion tunnel prevents lithium ions from solvating and co-intercalating with the carbon negative electrode, such as organic solvents in electrolytes with a large molecular weight that move together with the lithium ion and dissolve the structure of the carbon negative electrode. .

  Therefore, in order to improve the high temperature cycle characteristics and low temperature output of the lithium secondary battery, a strong SEI film must be formed on the negative electrode of the lithium secondary battery. Once the SEI film is formed at the time of first charge, the reaction between lithium ions and the negative electrode or other substances is prevented during repeated charging and discharging of the battery after that, and between the electrolyte and the negative electrode. It will serve as an ion tunnel that allows only lithium ions to pass through.

  In general, a two-component electrolyte based on ethylene carbonate (EC) is used as an electrolyte of a lithium ion battery. However, since EC has a high melting point, its use temperature is limited, and it can lead to considerable battery performance degradation at low temperatures.

  The problem to be solved by the present invention is not only to improve low-temperature output characteristics, but also to improve the high-temperature cycle characteristics, output characteristics after high-temperature storage, capacity characteristics and swelling characteristics non-aqueous for lithium secondary batteries An electrolytic solution and a lithium secondary battery including the same are provided.

  In order to solve the problems to be solved, the present invention includes i) a non-aqueous organic solvent containing propylene carbonate (PC); and ii) lithium bis (fluorosulfonyl) imide (LiFSI). A non-aqueous electrolyte is provided.

  The present invention also provides a lithium secondary battery including a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; a separator interposed between the positive electrode and the negative electrode; and the non-aqueous electrolyte.

  According to the non-aqueous electrolyte of the present invention, a low-temperature output characteristic can be improved by forming a strong SEI film at the negative electrode during initial charging of a lithium secondary battery including the same, as well as high-temperature cycle characteristics, after high-temperature storage. Output characteristics, capacitance characteristics, and swelling characteristics can be improved.

6 is a graph showing results of measuring low-temperature output characteristics associated with SOC (charge depth) of lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 based on Experimental Example 1. FIG. 6 is a graph showing results of measuring capacity characteristics according to the number of cycles of lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 based on Experimental Example 2. FIG. It is a graph which shows the result of having measured the output characteristic in 50% of SOC accompanying a storage period after high temperature storage of the lithium secondary battery of Example 1 and Comparative Examples 1 to 3 based on Experimental Example 3. It is a graph which shows the result of having measured the capacity | capacitance characteristic accompanying a storage period after high temperature storage of the lithium secondary battery of Example 1 and Comparative Examples 1 to 3 based on Experimental Example 4. 6 is a graph showing results of measuring swelling characteristics associated with a storage period after high-temperature storage of lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 based on Experimental Example 5. FIG. 7 is a graph showing results of measuring low-temperature output characteristics associated with SOC (charge depth) of lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 based on Experimental Example 6. FIG. 10 is a graph showing results of measuring capacity characteristics according to the number of cycles of lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 based on Experimental Example 7. FIG. It is a graph which shows the result of having measured the capacity | capacitance characteristic with a storage period after high temperature storage of the lithium secondary battery of Examples 1 and 2 and the comparative example 4 based on Experimental example 8. FIG.

  Hereinafter, the present invention will be described in more detail in order to facilitate understanding of the present invention. Terms and words used in this specification and claims should not be construed to be limited to ordinary and dictionary meanings, and the inventor should describe his invention in the best possible manner. Based on the principle that the concept of terms can be appropriately defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

  The non-aqueous electrolyte according to an embodiment of the present invention may include a non-aqueous organic solvent including propylene carbonate (PC) and lithium bis (fluorosulfonyl) imide (LiFSI).

  According to one embodiment of the present invention, when lithium bisfluorosulfonylimide is used in combination under a solvent of propylene carbonate (PC), a low-temperature output characteristic is improved by forming a strong SEI film on the negative electrode during initial charging. Of course, to suppress the decomposition of the positive electrode surface that can occur during high-temperature cycle operation of 55 ° C or higher, to prevent the oxidation reaction of the electrolyte, to suppress the swelling phenomenon and to improve the capacity of the battery Can do.

  In general, a two-component electrolyte based on ethylene carbonate (EC) has been used as an electrolyte of a lithium ion battery. However, since EC has a high melting point, its use temperature is limited, and the battery performance is considerably lowered at low temperatures. On the other hand, an electrolyte containing propylene carbonate has an advantage that it can perform an excellent role as an electrolyte while having a wider temperature range than an electrolyte of ethylene carbonate.

However, when propylene carbonate is used together with a lithium salt such as LiPF ₆ as a solvent, propylene carbonate is a process of forming an SEI film in a lithium ion battery using a carbon electrode, and lithium ions solvated by propylene carbonate are formed in the carbon layer. An enormous volume of irreversible reaction may occur during the intercalation process. This can cause problems such as high temperature cycling characteristics that degrade battery performance.

  Further, when lithium ions solvated with propylene carbonate are inserted into the carbon layer constituting the negative electrode, exfoliation of the carbon surface layer can proceed. Such exfoliation may occur when a gas generated when the solvent is decomposed between the carbon layers induces a large twist between the carbon layers. Such peeling of the carbon surface layer and decomposition of the electrolytic solution can be continued, and thus, when using an electrolytic solution containing propylene carbonate together with a carbon-based negative electrode material, effective SEI is not generated, and lithium ion May not be inserted.

In the present invention, the problem of low-temperature characteristics due to the use of ethylene carbonate is solved by using propylene carbonate having a low melting point, and the above-described problems when using both propylene carbonate and a lithium salt such as LiPF ₆ are solved. This can be solved by combining these using sulfonylimide.

  According to an embodiment of the present invention, the concentration of the lithium bisfluorosulfonylimide in the non-aqueous electrolyte is preferably 0.1 mole / l to 2 mole / l, and 0.6 mole / l to 1.5 mole. More preferred is / l. If the concentration of the lithium bisfluorosulfonylimide is less than the above range, the effect of improving the low-temperature output of the battery and improving the high-temperature cycle characteristics is slight, and when the concentration of the lithium bisfluorosulfonylimide exceeds the above range When the battery is charged / discharged, a side reaction in the electrolyte may occur excessively, and a swelling phenomenon may occur.

In order to further prevent such a side reaction, the nonaqueous electrolytic solution of the present invention may further contain a lithium salt. As the lithium salt, a lithium salt usually used in the art can be used. For example, LiPF ₆ , LiBF ₄ , LiSbF ₆ , LiAsF ₆ , LiClO ₄ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ One selected from the group consisting of SO ₂ ) ₂ , CF ₃ SO ₃ Li, LiC (CF ₃ SO ₂ ) ₃ and LiC ₄ BO ₈ , or a mixture of two or more of these may be included.

  According to one embodiment of the present invention, by adjusting the mixing ratio of the lithium salt and lithium bisfluorosulfonylimide, the low temperature output characteristics, the capacity characteristics after high temperature storage and the cycle characteristics of the lithium secondary battery can be improved. it can.

  Specifically, the mixing ratio of the lithium salt and lithium bisfluorosulfonylimide is preferably 1: 6 to 9 in molar ratio. If the mixing ratio of the lithium salt and lithium bisfluorosulfonylimide is outside the range of the molar ratio, side reactions in the electrolyte may occur excessively during battery charging / discharging, and a swelling phenomenon may occur. . Specifically, when the mixing ratio of the lithium salt and lithium bisfluorosulfonylimide is less than 1: 6, the process of forming the SEI film in the lithium ion battery, and lithium ions solvated with propylene carbonate An enormous capacity irreversible reaction may occur in the process of inserting between the negative electrodes, improving the low-temperature output of the secondary battery by peeling the negative electrode surface layer (for example, the carbon surface layer) or decomposing the electrolyte, After high temperature storage, the effect of improving cycle characteristics and capacity characteristics may be slight.

  Meanwhile, as a non-aqueous organic solvent according to an embodiment of the present invention, propylene carbonate may be included in an amount of 5 to 60 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the non-aqueous organic solvent. . If the content of propylene carbonate is less than 5 parts by weight, a swelling phenomenon may occur in which gas is continuously generated due to decomposition of the positive electrode surface during a high-temperature cycle and the thickness of the battery is increased. If it exceeds, it may be difficult to form a strong SEI film on the negative electrode during initial charging.

  In addition to the propylene carbonate, the non-aqueous organic solvent that can be included in the non-aqueous electrolyte solution can minimize degradation due to oxidation reaction during the charge / discharge process of the battery, and has the desired characteristics together with the additive. There is no limit as long as it can be demonstrated.

  The non-aqueous organic solvent according to one embodiment of the present invention preferably does not contain ethylene carbonate (EC), such as ethyl propionate (EP), methyl propionate (Methyl Propionate; MP), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), ester Any one selected from the group consisting of organic, etheric and ketone organic solvents, or a mixture of two or more of these can be further included.

  Meanwhile, the non-aqueous electrolyte according to an embodiment of the present invention may further include a vinylidene carbonate compound and a sultone compound.

  The vinylene carbonate-based compound can serve to form an SEI film. The type of the vinylene carbonate-based compound is not limited as long as it can perform the above-described role, and for example, vinylene carbonate (VC), vinylene ethylene carbonate (VEC), or a mixture thereof. Can be included. Among these, it is particularly preferable to contain vinylene carbonate.

  In addition, the sultone-based compound that can be further included in one embodiment of the present invention can improve the low-temperature output and high-temperature cycle characteristics of the battery. The type of the sultone-based compound is not limited as long as it can perform the above-mentioned role. For example, the 1,3-propane sultone (PS), 1,4-butane sultone, Any one selected from the group consisting of 1,3-propene sultone, or a mixture of two or more thereof. Among these, it is particularly preferable to contain 1,3-propane sultone.

  Meanwhile, a lithium secondary battery according to an embodiment of the present invention includes a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; a separator interposed between the positive electrode and the negative electrode; and the non-aqueous electrolyte. Can be included.

Here, the positive active material may include a manganese-based spinel active material, a lithium metal oxide, or a mixture thereof. Further, the lithium metal oxide is selected from the group consisting of lithium-manganese oxide, lithium-nickel-manganese oxide, lithium-manganese-cobalt oxide, and lithium-nickel-manganese-cobalt oxide. More specifically, LiCoO ₂ , LiNiO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , Li (Ni _a Co _b Mn _c ) O ₂ (where 0 <a <1, 0 <b <1, 0 <c <1, a + b + c = 1), LiNi _1-Y Co _Y O ₂ , LiCo _1-Y Mn _Y O ₂ , LiNi _1-Y Mn _Y O ₂ (where 0 ≦ Y <1) , Li (Ni _a Co _b Mn _c ) O ₄ (0 <a <2, 0 <b <2, 0 <c <2, a + b + c = 2), LiMn _2-z Ni _z O ₄ , LiMn _2-z Co _z O ₄ (where 0 <Z <2) may be included.

  On the other hand, as the negative electrode active material, a carbon-based negative electrode active material such as crystalline carbon, amorphous carbon, or a carbon composite may be used alone or in combination of two or more, preferably as crystalline carbon Graphite carbon such as natural graphite and artificial graphite can be included.

The separator is a porous polymer film, for example, a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer. The porous polymer film manufactured by the molecule | numerator may be what was individual, or 2 or more types were laminated | stacked. In addition to this, a normal porous nonwoven fabric, for example, a nonwoven fabric made of high melting point glass fiber, polyethylene terephthalate fiber or the like can be used, but is not limited thereto.
[Mode for Carrying Out the Invention]

  Hereinafter, although an example and an experimental example are given and explained further, the present invention is not limited by these examples and an experimental example.

  [Production of non-aqueous electrolyte]

Based on the total amount of non-aqueous organic solvent and non-aqueous electrolyte having a composition of propylene carbonate (PC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) = 2: 4: 4 (volume ratio), LiPF ₆₀ 0.1 mole / l and 0.9 mole / l lithium bisfluorosulfonylimide (LiFSI), 3% by weight vinylene carbonate (VC) and 0.5% by weight 1,3-propane sultone (PS) were added to make the mixture non-aqueous. An electrolyte was produced.

[Manufacture of lithium secondary batteries]
96% by weight of a mixture of LiMn ₂ O ₄ and Li (Ni _0.33 Co _0.33 Mn _0.33 ) O ₂ as a positive electrode active material, 3% by weight of carbon black as a conductive material, and polyvinylidene fluoride as a binder A positive electrode mixture slurry was prepared by adding 3% by weight of ride (PVdF) to the solvent N-methyl-2-pyrrolidone (NMP). The positive electrode mixture slurry was applied to an aluminum (Al) thin film as a positive electrode current collector having a thickness of about 20 μm and dried to produce a positive electrode, and then a roll press was performed to produce a positive electrode.

  Further, a negative electrode active material was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive material to 96 wt%, 3 wt%, and 1 wt%, respectively, and adding them to NMP as a solvent. . The negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 μm, and dried to produce a negative electrode, and then a roll press was performed to produce a negative electrode.

  The positive electrode and negative electrode manufactured in this way were manufactured together with a PE separator by a conventional method, and then the manufactured non-aqueous electrolyte was injected to complete the manufacture of a lithium secondary battery.

In the same manner as in Example 1, except that LiPF ₆ 0.1 mole / l and lithium bisfluorosulfonylimide (LiFSI) 0.6 mole / l were used based on the total amount of the non-aqueous electrolyte. A non-aqueous electrolyte and a lithium secondary battery were manufactured.

[Comparative Example 1]
Using a non-aqueous organic solvent having a composition of ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) = 3: 3: 4 (volume ratio), LiPF ₆ was used alone as a lithium salt. Except for this, a non-aqueous electrolyte and a lithium secondary battery were produced in the same manner as in Example 1.

[Comparative Example 2]
Same as Example 1 except that a non-aqueous organic solvent having a composition of ethylene carbonate (EC): ethyl methyl carbonate (EMC): dimethyl carbonate (DMC) = 3: 3: 4 (volume ratio) was used. Thus, a non-aqueous electrolyte and a lithium secondary battery were produced.

[Comparative Example 3]
A non-aqueous electrolyte and a lithium secondary battery were manufactured in the same manner as in Example 1 except that LiPF ₆ was used alone as a lithium salt.

[Comparative Example 4]
In the same manner as in Example 1 except that LiPF ₆ 0.1 mole / l and lithium bisfluorosulfonylimide (LiFSI) 0.5 mole / l were used based on the total amount of the non-aqueous electrolyte. A non-aqueous electrolyte and a lithium secondary battery were manufactured.

[Experiment 1]
<Low temperature output characteristics test>
The low temperature output was calculated by the voltage difference generated by discharging the lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 at −30 ° C. for 10 seconds at 0.5 C for each SOC (depth of charge). The results are shown in FIG.

  Referring to FIG. 1, the lithium secondary battery of Example 1 is superior in output characteristics from SOC 20% compared with the lithium secondary batteries in Comparative Examples 1 to 3, and the output characteristics are compared from SOC after 60%. It started to show a marked difference from the examples. When the SOC is 100%, the lithium secondary battery of Example 1 is about 1.2 to 1.4 times higher than the lithium secondary batteries of Comparative Examples 1 to 3, and the low temperature output characteristics are improved. I understand that.

  This can confirm that the low temperature characteristics can be remarkably improved by using propylene carbonate without using ethylene carbonate as the non-aqueous organic solvent.

[Experiment 2]
<High temperature (55 ° C) cycle characteristic test>
The lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 were charged at 1 C to 4.2 V / 38 mA under the condition of constant current / constant voltage (CC / CV) at 55 ° C., and then the constant current (CC) It discharged to 3C to 3.03V on condition, and the discharge capacity was measured. This was repeated in 1 to 900 cycles, and the measured discharge capacity is shown in FIG.

  As can be seen from FIG. 2, up to the 200th cycle, the lithium secondary battery of Example 1 according to the present invention showed a capacity retention similar to the lithium secondary batteries of Comparative Examples 1 to 3, From the 360th cycle onward, there was a significant difference in capacity retention.

  Therefore, the lithium secondary battery (Example 1) using a combination of propylene carbonate and lithium bisfluorosulfonylimide according to the example of the present invention is cycled at a high temperature condition of 55 ° C. as compared with Comparative Examples 1 to 3. It was found that the discharge capacity characteristics accompanying the characteristics are remarkably excellent.

[Experiment 3]
<Output characteristics after high temperature storage>
The lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 were stored at 60 ° C. for 14 weeks, and then the output was calculated by the voltage difference generated by discharging at 50 ° C. for 10 seconds at 5C. The results are shown in FIG.

  Referring to FIG. 3, the output characteristics at SOC 50% after storage at 60 ° C. are the same as those of the lithium secondary battery using the combination of propylene carbonate and lithium bisfluorosulfonylimide according to Example 1 of the present invention. Therefore, it can be confirmed that it is remarkably superior to Comparative Example 3. Specifically, in the case of Example 1, the output characteristics increased from the storage period of 2 weeks, and it can be confirmed that the storage characteristics increase and the output characteristics are continuously improved up to the storage period of up to 14 weeks or at high temperatures. . On the other hand, Comparative Examples 1 and 3 differed from Example 1 in terms of initial output characteristics, and showed a significant difference from the Example at the storage period of 14 weeks. In the case of Comparative Example 2, the initial output characteristics were similar to Example 1, but gradually decreased from the second week of the storage period, and in the same manner as in Comparative Examples 1 and 3 at the 14th week of the storage period. It showed a significant difference from 1.

[Experimental Example 4]
<Capacity characteristic test after high temperature storage>
After the lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 were stored at 60 ° C. for 14 weeks and then charged at a constant current / constant voltage (CC / CV) condition of 4.2 V / 38 mA at 1 C, the constant current Under the condition of (CC), the battery was discharged at 1 C to 3.0 V, and the discharge capacity was measured. The results are shown in FIG.

  Referring to FIG. 4, there was no difference in capacity characteristics between Comparative Examples 1 to 3 and Example 1 until the storage period of 2 weeks, but in the case of Comparative Examples 1 to 3 after the storage period of 4 weeks, the storage period increased. It can be seen that the capacity characteristics gradually decrease, and the difference between the capacity characteristics of Comparative Examples 1 to 3 and Example 1 gradually increases in Example 1 after the storage period of 8 weeks.

  Therefore, it can be confirmed that the lithium secondary battery of Example 1 has an effect of improving the capacity characteristics after high-temperature storage as compared with the lithium secondary batteries of Comparative Examples 1 to 3.

[Experimental Example 5]
<Swelling characteristics test after high temperature storage>
The lithium secondary batteries of Example 1 and Comparative Examples 1 to 3 were stored at 60 ° C. for 14 weeks and then stored at SOC 95%, and the thickness of the battery was measured. The results are shown in FIG.

  Referring to FIG. 5, in the case of the lithium secondary batteries of Comparative Examples 1 to 3, the thickness of the battery has been remarkably increased after the storage period of 2 weeks, whereas the lithium secondary battery of Example 1 is compared with the comparative examples and the like. The increase in thickness was small.

  This shows that by using propylene carbonate and lithium bisfluorosulfonylimide in combination, even if the storage period is increased after high temperature storage, the swelling suppression effect of the battery can be improved.

[Experimental Example 6]
<Low temperature output characteristics test with the molar ratio of LiPF ₆ and LiFSI>
In order to investigate the low temperature output characteristics according to the molar ratio of LiPF ₆ and LiFSI, the lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 were discharged at −30 ° C. for 10 seconds at 0.5 ° C. by SOC (depth of charge). Then, the low temperature output was calculated from the generated voltage difference. The results are shown in FIG.

Referring to FIG. 6, the lithium secondary battery of Example 1 in which the molar ratio of LiPF ₆ and LiFSI is 1: 9 is the lithium secondary battery of Comparative Example 4 in which the molar ratio of LiPF ₆ and LiFSI is 1: 5. Compared with the SOC, the output characteristics are remarkably excellent from 20% SOC, and the output characteristics start to show a marked difference from the lithium secondary battery of Comparative Example 4 after the SOC 60%.

The lithium secondary battery of Example 2 in which the molar ratio of LiPF ₆ and LiFSI is 1: 6 is lower than that of the lithium secondary battery of Example 1 in which the molar ratio of LiPF ₆ and LiFSI is 1: 9. Output characteristics decreased.

On the other hand, the lithium secondary battery of Example 2 in which the molar ratio of LiPF ₆ and LiFSI is 1: 6 is similar to the lithium secondary battery of Comparative Example 4 in which the molar ratio of LiPF ₆ and LiFSI is 1: 5. Although the characteristics are shown, it can be seen that the low-temperature output characteristics are improved as compared with the lithium secondary battery of Comparative Example 4 from SOC 90% or more.

Therefore, it can be confirmed that the low temperature output characteristics of the lithium secondary battery can be improved by adjusting the molar ratio of LiPF ₆ and LiFSI.

[Experimental Example 7]
<High temperature (55 ° C) cycle characteristics test with molar ratio of LiPF ₆ and LiFSI>
In order to investigate the high temperature (55 ° C.) cycle characteristics associated with the molar ratio of LiPF ₆ and LiFSI, the lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 were subjected to constant current / constant voltage (CC / CV) at 55 ° C. ) Was charged at 1 C to 4.2 V / 38 mA under the condition of 3), then discharged at 3 C to 3.03 V under the constant current (CC) condition, and the discharge capacity was measured. This was repeated for 1 to 1000 cycles, and the measured discharge capacity is shown in FIG.

  As can be seen in FIG. 7, until about the 70th cycle, the lithium secondary battery of Example 1 according to the present invention showed a capacity retention similar to the lithium secondary battery of Comparative Example 4, but about 70 From the second cycle to the 1000th cycle, there was a remarkable difference of about 7% or more in capacity retention.

  On the other hand, the lithium secondary battery of Example 2 showed a significant difference from Comparative Example 4 in capacity retention until the approximately 600th cycle. It can be confirmed that the slope of the graph of the lithium secondary battery of Comparative Example 4 significantly decreases as the number of cycles increases. In addition, the lithium secondary battery of Example 2 shows a difference of about 3 to 5% in capacity retention from the 900th cycle to the 1000th cycle as compared with the lithium secondary battery of Comparative Example 4. I understand.

Therefore, when the molar ratio of LiPF ₆ and LiFSI is 1: 6 to 1: 9, it is confirmed that the high temperature (55 ° C.) cycle characteristics of the lithium secondary battery are remarkably superior to those outside this range. be able to.

[Experimental Example 8]
<Capacitance characteristic test after high temperature storage (60 ° C.) according to the molar ratio of LiPF ₆ and LiFSI>
In order to confirm the capacity characteristic test after high temperature storage (60 ° C.) according to the molar ratio of LiPF ₆ and LiFSI, the lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 were stored at 60 ° C. for 14 weeks. After charging at 1 C to 4.2 V / 38 mA under constant current / constant voltage (CC / CV) conditions, the battery was discharged at 1 C to 3.0 V under constant current (CC) conditions, and the discharge capacity was measured. The results are shown in FIG.

  Referring to FIG. 8, there was no difference in the capacity characteristics of the lithium secondary batteries of Examples 1 and 2 and Comparative Example 4 until the storage period of 1 week, but the lithium secondary batteries of Examples 1 and 2 after the storage period of 2 weeks. It can be seen that the battery has a larger difference in capacity characteristics than the lithium secondary battery of Comparative Example 4.

  When specifically examined, the slope of the graph of the lithium secondary battery of Example 1 was gentle until the storage period of 14 weeks. As a result, the lithium secondary battery of Example 1 showed a difference in capacity retention up to about 6% or more compared with the lithium secondary battery of Comparative Example 4 at the 14-week storage period.

  On the other hand, it can be confirmed that the capacity characteristic of the lithium secondary battery of Comparative Example 4 gradually decreases as the storage period increases, while the slope of the graph decreases significantly after the storage period of 2 weeks.

Therefore, by adjusting the molar ratio of LiPF ₆ and LiFSI, the high temperature storage characteristics of the lithium secondary battery can be improved, especially when the molar ratio of LiPF ₆ and LiFSI is 1: 6 to 1: 9. It can be confirmed that the high-temperature storage characteristics of the lithium secondary battery are remarkably superior compared to the case outside the range.

  When applied to a lithium secondary battery, the non-aqueous electrolyte according to an embodiment of the present invention improves low-temperature output characteristics by forming a strong SEI film at the negative electrode during initial charging of the lithium secondary battery. Needless to say, the high-temperature cycle characteristics, the output characteristics after high-temperature storage, the capacity characteristics, and the swelling characteristics can be improved, so that it can be usefully applied to a lithium secondary battery.

Claims (11)

i) a non-aqueous organic solvent comprising a carbonate-based solvent; and ii) a lithium salt and lithium bisfluorosulfonylimide (LiFSI),
The carbonate solvent comprises propylene carbonate (PC) , ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC),
The volume ratio of propylene carbonate (PC), ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) is 2: 4: 4,
The mixing ratio of the lithium bisfluorosulfonylimide and the lithium salt is 1 molar ratio: 6 to 1: 9 der is,
The non-aqueous electrolytic solution is characterized in that the lithium bisfluorosulfonylimide has a concentration in the non-aqueous electrolytic solution of 0.6 mole / l to 1.5 mole / l . The non-aqueous electrolyte according to claim 1, wherein the non-aqueous electrolyte does not contain ethylene carbonate (EC). The non-aqueous electrolyte according to claim 1 or 2 , wherein the content of the propylene carbonate is 5 to 60 parts by weight based on 100 parts by weight of the non-aqueous organic solvent. The non-aqueous electrolyte according to claim 3 , wherein the content of the propylene carbonate is 10 to 50 parts by weight based on 100 parts by weight of the non-aqueous organic solvent. The nonaqueous electrolytic solution according to any one of claims 1 to 4 , wherein the nonaqueous electrolytic solution further includes a vinylene carbonate compound and a sultone compound. The non-aqueous electrolyte according to claim 5 , wherein the vinylene carbonate-based compound includes vinylene carbonate, vinylene ethylene carbonate, or a mixture thereof. The sultone-based compound is selected from the group consisting of 1,3-propane sultone, 1,4-butane sultone, and 1,3-propene sultone, or two or more of these The non-aqueous electrolytic solution according to claim 5 or 6 , comprising a mixture. The lithium _{salt, LiPF 6, LiBF 4, LiSbF} 6, LiAsF 6, LiClO 4, LiN (C 2 F 5 SO 2) 2, LiN (CF 3 SO 2) 2, CF 3 SO 3 Li, LiC (CF 3 SO _{2) 3} and LiC ₄ one selected from the group consisting of BO _8, or a non-aqueous electrolyte solution according to claim 1, characterized in that it comprises these among two or more thereof. A positive electrode comprising a positive electrode active material;
A negative electrode comprising a negative electrode active material;
A separator interposed between the positive electrode and the negative electrode; and a lithium secondary battery comprising the nonaqueous electrolytic solution according to any one of claims 1 to 8 . The lithium secondary battery according to claim 9 , wherein the negative electrode active material is a carbon-based negative electrode active material. 11. The lithium secondary battery according to claim 10 , wherein the negative electrode active material includes graphite carbon.

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